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Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation

Transverse nuclear spin relaxation is a sensitive probe of chemical exchange on timescales on the order of microseconds to milliseconds. Here we present an experiment for the simultaneous measurement of the relaxation rates of two quadruple-quantum transitions in [Formula: see text] CH [Formula: see...

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Autores principales: Waudby, Christopher A., Christodoulou, John
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Copernicus GmbH 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10583286/
https://www.ncbi.nlm.nih.gov/pubmed/37905227
http://dx.doi.org/10.5194/mr-2-777-2021
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author Waudby, Christopher A.
Christodoulou, John
author_facet Waudby, Christopher A.
Christodoulou, John
author_sort Waudby, Christopher A.
collection PubMed
description Transverse nuclear spin relaxation is a sensitive probe of chemical exchange on timescales on the order of microseconds to milliseconds. Here we present an experiment for the simultaneous measurement of the relaxation rates of two quadruple-quantum transitions in [Formula: see text] CH [Formula: see text] -labelled methyl groups. These coherences are protected against relaxation by intra-methyl dipolar interactions and so have unexpectedly long lifetimes within perdeuterated biomacromolecules. However, these coherences also have an order of magnitude higher sensitivity to chemical exchange broadening than lower order coherences and therefore provide ideal probes of dynamic processes. We show that analysis of the static magnetic field dependence of zero-, double- and quadruple-quantum Hahn echo relaxation rates provides a robust indication of chemical exchange and can determine the signed relative magnitudes of proton and carbon chemical shift differences between ground and excited states. We also demonstrate that this analysis can be combined with established Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion measurements, providing improved precision in parameter estimates, particularly in the determination of [Formula: see text] H chemical shift differences.
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spelling pubmed-105832862023-10-30 Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation Waudby, Christopher A. Christodoulou, John Magn Reson (Gott) Research Article Transverse nuclear spin relaxation is a sensitive probe of chemical exchange on timescales on the order of microseconds to milliseconds. Here we present an experiment for the simultaneous measurement of the relaxation rates of two quadruple-quantum transitions in [Formula: see text] CH [Formula: see text] -labelled methyl groups. These coherences are protected against relaxation by intra-methyl dipolar interactions and so have unexpectedly long lifetimes within perdeuterated biomacromolecules. However, these coherences also have an order of magnitude higher sensitivity to chemical exchange broadening than lower order coherences and therefore provide ideal probes of dynamic processes. We show that analysis of the static magnetic field dependence of zero-, double- and quadruple-quantum Hahn echo relaxation rates provides a robust indication of chemical exchange and can determine the signed relative magnitudes of proton and carbon chemical shift differences between ground and excited states. We also demonstrate that this analysis can be combined with established Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion measurements, providing improved precision in parameter estimates, particularly in the determination of [Formula: see text] H chemical shift differences. Copernicus GmbH 2021-11-03 /pmc/articles/PMC10583286/ /pubmed/37905227 http://dx.doi.org/10.5194/mr-2-777-2021 Text en Copyright: © 2021 Christopher A. Waudby and John Christodoulou https://creativecommons.org/licenses/by/4.0/This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/4.0/
spellingShingle Research Article
Waudby, Christopher A.
Christodoulou, John
Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title_full Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title_fullStr Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title_full_unstemmed Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title_short Analysis of conformational exchange processes using methyl-TROSY-based Hahn echo measurements of quadruple-quantum relaxation
title_sort analysis of conformational exchange processes using methyl-trosy-based hahn echo measurements of quadruple-quantum relaxation
topic Research Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10583286/
https://www.ncbi.nlm.nih.gov/pubmed/37905227
http://dx.doi.org/10.5194/mr-2-777-2021
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